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UNIVERSITI PUTRA MALAYSIA

SYNTHESIS OF HYDROXYAPATITE AND FLUORAPATITE NANOPARTICLES WITH DIFFERENT AMOUNTS OF

FLUORIDE USING SOL-GEL METHOD

POONEH KIA

FS 2017 40

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NANOPARTICLES WITH DIFFERENT AMOUNTS OF FLUORIDE USING SOL-GEL METHOD

By

POONEH KIA

Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia, in Fulfillment of the Requirements for the Degree of

Master of Science

April 2017

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COPYRIGHT

All material contained within the thesis, including without limitation text, logos, icons, photographs and all other artwork, is copyright material of University Putra Malaysia unless otherwise stated. Use may be made of any material contained within the thesis for non-commercial purpose from the copyright holder. Commercial use of material may only be made with the express, prior, written permission of University Putra Malaysia.

Copyright © Universiti Putra Malaysia

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DEDICATION

To God, who gave me life and strength

To my family. A special feeling of gratitude to my loving parents, Homa Taghavi and Gholam Hossein Kia, whose words of encouragement and push for tenacity

ring in my ears, for all their love, sacrifices and faith and for their bless full prayers. To my dear sister Taraneh Kia, who is very special persons for me.

To my husband Ali Heidar Zolfaghari who stayed with me in difficult times and

never left my side.

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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfillment of the requirement for the Degree of Master of Science

SYNTHESIS OF HYDROXYAPATITE AND FLUORAPATITE NANOPARTICLES WITH DIFFERENT AMOUNTS OF

FLUORIDE USING SOL-GEL METHOD

By

POONEH KIA

April 2017

Chairman : Professor Mansor B Ahmad, PhD Faculty : Science

Fluorapatite (FA) has been indicated as well alternative to pure hydroxyapatite (HA) in many reactions. Since the thermal decomposition and the poor corrosion resistance in an acid environment have restricted the applications of HA, as a solution, fluoride substitution in the structure of HA can improve the chemical stability and biocompatibility of HA nanoparticles. Therefore, FA nano particles can be used as a bioactive substance in the body, especially the teeth implants. Fluorhydroxyapatite (FHA) and FA nanoparticles were synthesized by adding the different amount of fluorine to the structure of HA using sol–gel method. Final products were characterized and optimized after different heat treatments of 700 °C to 1300 °C in order to improve its crystallinity. The aim of this study is to utilize sodium alginate (SA) as a bio-stabilizer in order to have the better precipitate which leads to having better crystallinity and smaller particle size. Calcium nitrate tetrahydrate, Ca(NO3)2•4H2O, diammonium phosphate (NH4)2HPO4, ammonium fluoride, NH4F, were used as precursors of Ca, P and F respectively with the ratio of 1:67 Ca/P, and pH kept between 10 - 11. The presence of HA and FA phase investigated by the results of x-ray diffraction (XRD) spektroscopy which confirmed the presence of all fluoride peaks more than 0.6 wt% in the structure of FA. Fourier-transform infra-red (FTIR) spectrum showed that fluoride was substituted by hydroxyl group in the samples which contained more than 0.6 wt% fluoride, while this could be describe by two evidences; disappearing the hydroxyl group at 3600 cm-1 and emerged of fluoride peak at 631 cm-1. Thermal gravimetric analysis (TGA) indicated that by increasing the amount of fluoride in the structure of apatite to more than 0.6 wt%, inevitably thermal stability increased. FA samples sintered at 700 ᴼC were observed to have average sizes of 50 nm and rod like shape, which were determined by TEM and SEM, respectively. Moreover, similar samples with SA indicated smaller particle size compared to those of without SA. From another aspect, SEM and TEM, samples sintered 1300 ᴼC indicated smaller size and finest nano rod like shape, 25

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nm width and 8 nm in lengths for FA samples with SA. In conclusion, by using SA within the sol-gel method and increasing the amount of fluoride more than 0.6 wt% in the structure of HA, particle size significantly decreased and thermal stability remarkably improved.

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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai memenuhi keperluan untuk Ijazah Sarjana Sains

SINTESIS NANOPARTIKEL HIDROKSIAPATIT DAN FLUORAPATIT DENGAN KANDUNGAN FLUORIN YANG BERBEZA MELAUI KAEDAH

SOL-GEL

Oleh

POONEH KIA

April 2017

Pengerusi : Profesor Mansor B Ahmad, PhD Fakulti : Sains

Fluorapatit (FA) telah ditunjukkan sebagai alternatif yang baik kepada hidroksiapatit tulen (HA) dalam banyak tindak balas. Oleh kerana penguraian terma dan rintangan kakisan yang rendah dalam persekitaran berasid telah mengehadkan keberkesanan HA, sebagai penyesaian, fluorida yang digunakan sebagai pengganti dalam struktur HA untuk meningkatkan kestabilan kimia dan keserasianbio nanopartikel HA. Justeru, nanopartikel FA boleh digunakan sebagai bahan bioaktif dalam badan, terutamanya dalam implan gigi. Fluorhidroksiapatit (FHA) dan nanopartikel FA telah disintesis dengan menambah amaun fluorin yang berbeza kepada struktur HA dengan menggunakan kaedah sol-gel. Produk akhir diciri dan dioptimumkan selepas rawatan haba yang berbeza dijalankan pada suhu 700 ° C hingga 1300 ° C untuk meningkatkan penghablurannya. Tujuan kajian ini adalah untuk menggunakan natrium alginat (SA) sebagai penstabilbio untuk mendapatkan mendakan yang lebih baik bagi menghasilkan penghabluran yang lebih baik dan saiz zarah yang lebih kecil. Kalsium nitrat tetrahidrat, Ca(NO3)2•4H2O, diamonium fosfat (NH4)2HPO4, amonium fluorida, NH4F, telah digunakan masing-masing sebagai pendahulu Ca, P dan F dengan nisbah 1:67 Ca/P, serta pH dikekalkan antara 10 - 11. Kehadiran HA dan fasa FA disiasat oleh keputusan spektroskopi pembelauan X-ray yang mengesahkan kehadiran semua puncak ion fluorida lebih daripada 0.6 wt% dalam struktur FA. Spektrum inframerah jelmaan Fourier (FTIR) menunjukkan fluorida telah digantikan dengan kumpulan hidroksil dalam sampel yang mengandungi lebih daripada 0.6 wt% fluorida, hal ini boleh diterangkan dengan dua bukti; penghapusan kumpulan hidroksil pada 3600 cm-1 dan kemunculan serapan fluorida pada 631 cm-

1. Analisis gravimetri terma (TGA) menunjukkan, dengan menaikkan amaun fluoridadalam struktur apatit lebih daripada 0.6 wt%, kestabilan haba meningkat. Sampel FA yang disinter pada 700 oC menunjukkan purata saiz 50 nm dan berbentuk rod, masing-masing telah ditentukan oleh mikroskopi elektron imbasan (SEM) dan mikroskopi elektron penghantaran (TEM). Selain itu, sampel yang sama dengan SA

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menunjukkan saiz zarah yang lebih kecil berbanding dengan sampel tanpa SA. Dari aspek lain, SEM dan TEM, sampel yang disinter pada 1300 ᴼC menunjukkan ukuran yang lebih kecil dan bentuk rod nano terbaik, lebar 25 nm dan 8 nm panjang untuk sampel FA dengan SA. Kesimpulannya dengan menggunakan SA dalam kaedah sol-gel dan meningkatkan amaun fluorida dalam struktur HA kepada lebih daripada 0.6 wt%, saiz partikel berkurangan secara ketara dan kestabilan haba meningkat dengan luar biasa.

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ACKNOWLEDGEMENTS

First of all, I will like to give praise to Almighty God for the wisdom and determination that he has bestowed upon me during this research project, and indeed, for keeping me healthy and safe throughout my life. I would like to express my sincere gratitude to my supervisor, Prof. Dr. Mansor Ahmad for his guidance and support throughout this study, especially for his countless hours of reflecting, reading, encouraging, and most of all patience throughout the entire process. I would also like to thank my committee members: Prof. Mansor B Ahmad, Prof. Mohd Zobir Hussein who were more than generous with their expertise and precious time. I would like to acknowledge my school division for allowing me to conduct my research and providing all the necessary assistance requested. Special thanks are also given to all the staffs of development and human resources department for their support. I would like to express my deepest gratitude to Dr. Kamyar Shameli, Katayoon Kalantari for sharing with me their knowledge and giving their precious time to help me achieve my aim. Appreciation is also given to my good family friend Mr DR Hajibeigi, my dear friends katayoon, Zahra and Hajar for their help encouragement which keep me going and wish them all the best in their life. Some of people are like the key in my life that without them all doors is locked; they are my parents, my merciful mother and father and my beloved husband. They always support, encourage and help me to achieve my goal. My grateful thanks goes to my dear husband Ali who encouraging me always to reach to my goals and specially thanks to my sister Taraneh from thousand miles away my God keep them safe and secure. I always thank God for having them. I want to give them my deepest acknowledge and thankfulness.

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This thesis was submitted to the Senate of the Universiti Putra Malaysia and has been accepted as fulfillment of the requirement for the degree of Master of Science.The members of the Supervisory Committee were as follows: Mansor B Ahmad, PhD Professor Faculty of Science Universiti Putra Malaysia (Chairman) Mohd Zobir Hussein, PhD Professor Faculty of Science Universiti Putra Malaysia (Member)

ROBIAH BINTI YUNUS, PhD Professor and Dean School of Graduate Studies Universiti Putra Malaysia Date:

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Declaration by graduate student I hereby confirm that: this thesis is my original work; quotations, illustrations and citations have been duly referenced; this thesis has not been submitted previously or concurrently for any other degree

at any institutions; intellectual property from the thesis and copyright of thesis are fully-owned by

Universiti Putra Malaysia, as according to the Universiti Putra Malaysia (Research) Rules 2012;

written permission must be obtained from supervisor and the office of Deputy Vice-Chancellor (Research and innovation) before thesis is published (in the form of written, printed or in electronic form) including books, journals, modules, proceedings, popular writings, seminar papers, manuscripts, posters, reports, lecture notes, learning modules or any other materials as stated in the Universiti Putra Malaysia (Research) Rules 2012;

there is no plagiarism or data falsification/fabrication in the thesis, and scholarly integrity is upheld as according to the Universiti Putra Malaysia (Graduate Studies) Rules 2003 (Revision 2012-2013) and the Universiti Putra Malaysia (Research) Rules 2012. The thesis has undergone plagiarism detection software

Signature: __________________________________ Date: ________________ Name and Matric No: Pooneh Kia , GS38330

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Declaration by Members of Supervisory Committee This is to confirm that: the research conducted and the writing of this thesis was under our supervision; supervision responsibilities as stated in the Universiti Putra Malaysia

(Graduate Studies) Rules 2003 (Revision 2012-2013) were adhered to.

Signature: Name of Chairman of Supervisory Committee:

Professor Dr. Mansor B Ahmad

Signature:

Name of Member of Supervisory Committee:

Professor Dr. Mohd Zobir Hussein

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TABLE OF CONTENTS

Page ABSTRACT iABSTRAK iiiACKNOWLEDGEMENTS vAPPROVAL viDECLARATION viiiLIST OF FIGURES xiiLIST OF ABBREVIATIONS xiv

CHAPTER 1 INTRODUCTION 1 1.1 Background 1 1.2 Aim of Research 2 1.3 Problem Statement 3 1.4 Objectives 3 2 LITERATURE REVIEW 5 2.1 Nanoparticles 5 2.2 Global Biomaterials Market 5 2.3 Bone Composition 6 2.4 Apatite 7 2.4.1 Apatite Structure 8 2.4.2 Apatite Substitutions 9 2.5 Calcium Orthophosphate 11 2.6 Hydroxyapatite and Fluorapatite 12 2.6.1 Hydroxyapatite 12 2.6.2 Fluorapatite 12 2.7 Structure of Hydroxyapatite and Fluorapatite 14 2.8 Methods for preparation of Hydroxyapatite 16 2.9 Sol-Gel Method 18 2.10 Fluorapatite Preparation Via the Sol-Gel Method 19 2.11 Chemical and Physical characterization of HA, FHA and

FA 20

2.12 Green Synthesis 21 2.12.1 Stabilizers 21 2.12.2 Sodium Alginate 22 2.13 Applications 23 3 MATERIALS AND METHODS 24 3.1 Materials 24 3.2 Methods 25 3.2.1 Preparation of HA and FA by Sol-Gel Method 25 3.2.2 Preparation of HA and FA with Sodium Alginate

by Sol-Gel Method 28

3.3 Characterization 30

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3.3.1 X-Ray Diffraction 30 3.3.2 Field Emission Scanning Electron Microscopy 30 3.3.3 Transmission Electron Microscopy 30 3.3.4 Energy Dispersive X–ray Spectroscopy 30 3.3.5 Fourier transformed –Infrared Spectroscopy 31 3.3.6 TGA of Dried Precipitates 31 4 RESULTS AND DISCUSSION 32 4.1 Preparation of Hydroxyapatite and Fluorapatite with

different amount of fluorine by Sol-Gel method at 700 ᴼC 32

4.1.1 XRD of HA and FA with different Amount of Fluorine by Sol-Gel method at 700 ᴼC

32

4.1.2 FTIR of HA and FA with different Amount of Fluorine by Sol-Gel method at 700 ᴼC

35

4.1.3 TEM of HA and FA with different amount of Fluorine by Sol-Gel method at 700 ᴼC

37

4.1.4 FESEM of HA and FA with different amount of Fluorine by Sol-Gel method at 700 ᴼC

38

4.2 Preparation of Hydroxyapatite and Fluorapatite with different amount of fluorine with SA by Sol-Gel method at 700 ᴼC

41

4.2.1 XRD of HA and FA with different amount of F with SA by Sol-Gel method at 700 ᴼC

41

4.2.2 FESEM of HA and FA with different amount of Fluorine by Sol-Gel method at 700 ᴼC

43

4.2.3 TGA of HA,FHAs and FA with different amount of Fluorine with SA by Sol-Gel method at 700ᴼC

45

4.2.4 TEM of FA with SA by Sol-Gel method at 700 ᴼC 48 4.2.5 FESEM of HA and FA with different Amount of

Fluorine by Sol-Gel method at 700 ᴼC 49

4.3 Preparation of hydroxyapatite and fluorapatite with different amount of fluorine with SA by sol-gel method at 1300 ᴼC

52

4.3.1 TEM of FA with sodium alginate by sol-gel method at 1300 ᴼC

52

4.3.2 FESEM result for HA and FA with sodium alginate by sol –gel method at 1300ᴼC

53

5 CONCLUSION 56 5.1 Conclusion 56 5.2 Recommendations for future research 56 REFERENCES 57BIODATA OF STUDENT 65LIST OF PUBLICATIONS 66

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LIST OF FIGURES Figure Page 2.1 Bioapatite’s nano crystals arrangement towards the collagen

micro fibrils 8

2.2 Hydroxyapatite atomic networks within for bioapatite. pattern (A)

down the c-axis, pattern (B) vertical to the c-axis 9

2.3 Schematic representation of an HA unit cell 14 2.4 (a) Structure of FHA with OH− groups, F− ions. (b) Difference

between HA and FHA structures 15

2.5 Chemical structure of sodium alginate 22 4.1 XRD of synthesized samples: (a) HA,(b) FHA0.2 wt%, (c) FHA

0.4 wt%,(d) FHA 0.6 wt%, (e) FHA 0.8 wt% and (f) FA by sol-gel method 700 ᴼC

34

4.2 FTIR transmittance spectra of synthesized samples: (a) HA,(b)

FHA0.2 wt%, (c) FHA 0.4 wt%,(d) FHA 0.6 wt%, (e) FHA 0.8 wt% and (f) FA by sol-gel method 700 ᴼC

36

4.3 TEM micrograph of HA (a) and HA histogram (b) by sol-gel

method 700ᴼ ᴼC 37

4.4 TEM micrographof (a) FHA0.2 wt%, (b) FHA 0.4 wt%,(c) FHA

0.6 wt%, (d) FHA 0.8 wt% and FA by sol-gel method 700 ᴼC 38

4.5 TEM micrograph of (a) FA and FA histogram by sol-gel method

700 ᴼC 38

4.6 FESEM results of FA (a) and FA EDX (b) by Sol_Gel method at

700 ᴼC 39

4.7 FESEM results of HA(a) EDX (b) result of HA and FHA (0.2

wt% and 0.6 wt%) by Sol_Gel method at 700 ᴼC 40

4.8 FESEM results of FHA (0.2 wt% (a) , 0.4 wt% (b) ,0.6 wt% (c)

and 0.8 wt% (d)) and their EDX result of by Sol_Gel method at 700 ᴼC

40

4.9 XRD of synthesized (f) HA, (e) FHA 0.2 wt%, (d) FHA 0.4 wt%,

(c) FHA 0.6 wt%, (b) FHA 0.8 wt% and (a) FA with Sodium Alginate by sol-gel method at 700 ᴼC

42

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4.10 FTIR transmittance spectra of synthesized samples; (f) HA, (e) FHA0.2 wt%,(d) FHA 0.4 wt%, (c) FHA 0.6 wt%, (b) FHA 0.8 wt% and (a) FA with Sodium Alginate by sol-gel method 700 ᴼC

44

4.11 TGA pattern of HA (a) and TGA patterns of FHA0.2wt%, FHA

0.4wt%, FHA 0.6wt%, FHA 0.8wt% and FA (b) by sol-gel method 700 ᴼC

46

4.12 TGA pattern of HA and its weight loss by sol-gel method 700 ᴼC 47 4.13 TGA pattern of FA and its weight loss by sol-gel method 700 ᴼC 47 4.14 TEM micrograph of (a) FA and FA histogram (b), with SA by sol-

gel method 700 ᴼC 48

4.15 TEM micrograph of HA (a) and HA histogram (b) with SA by sol-

gel method 700 ᴼC 49

4.16 TEM micrograph of FHAs (0.2 wt% (a), 0.4 wt% (b),0.6 wt% (c)

and 0.8 wt% (d))with SA by sol-gel method 700 ᴼC 49

4.17 FESEM results of FA (a) and EDX result of FA (b) with Sodium

alginate by Sol_Gel method at 700 ᴼC 50

4.18 FESEM results of FHAs (0.2 wt% (a), 0.4 wt% (b),0.6 wt% (c)

and 0.8 wt% (d))and EDX result of FHAs with Sodium alginate by Sol_Gel method at 700 ᴼC

51

4.19 FESEM results of HA (a) EDX (b) result of HA with Sodium

alginate by Sol_Gel method at 700 ᴼC 51

4.20 TEM micrograph of FA with different magnification of 500nm (a)

and 50 nm (b) and the histogram (c) with SA by sol-gel method 1300 ᴼC

53

4.21 FESEM result of FA (a) and EDX FA (b) with Sodium alginate

by Sol_Gel method at 1300 ᴼC 54

4.22 FESEM results of HA (a) EDX (b) result of HA with Sodium

alginate by Sol_Gel method at 1300 ᴼC 55

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LIST OF ABBREVIATIONS HA Hydroxyapatite

FHA Fluorhydroxyapatite

FA Fluorapatite

SA Sodium Alginate

XRD X-ray Diffraction

TEM Transmission Electron Microscopy

SEM Scanning Electron Microscopy

FTIR Fourier Transform Infrared Spectroscopy

TGA Thermal Gravimetric Analysis

TCP Tricalcum Phosphate

CHA Carbonate Hydroxyapatite

TFA Trifluor acetic acid

FESEM Field Emission Scanning Electron Microscope

TEA Triethanolamine

EDX Energy-Dispersive X-Ray Spectroscopy

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CHAPTER 1

INTRODUCTION

1.1 Background Nanotechnology science currently is one of the prominent challenging areas of scientific searches due to its nanoscale level in a wide range of subjects (Paul & Robeson, 2008). Beyond these various interactions in chemical fields what are impressive are the surface areas and properties, as nanosized components play an important role by providing remarkable surface areas (Hussain et al., 2006). Nanotechnology is greatly dependent on the size of nanoparticles, while the dimensions of particles have prominent effects on their specific features and properties (Yun et al., 2008). Irrespective of the small and tiny dimensions of nanoparticles, large surface areas to volume ratio, high energy in the relative surface, spatial confinements and decreasing the imperfections are some of the significant features of nanoparticles. Bulks and atoms materials, in contrast, are deprived of these substantial aspects (Jortner & Rao, 2002). A tiny object which can perform like a whole unit in terms of its transport and properties is an obvious illustration of a particle that can be described in the nanotechnology field. So far as the diameter is concerned, the size of the fine particles is in the range of 100 to 2500 nanometres, while in contrast, that of ultrafine particles is mentioned to be in the range of 1 to 100 nanometres, which resembles that of nanoparticles that are measured between two nanometres (Buzea, Pacheco, & Robbie, 2007) . At present, among the nanoparticles, synthesis of Hydroxyapatite and Fluorapatite nanoparticles has gained the attention of scientists owing to their usable properties, green methods and relatively low cost. Hydroxyapatite has known as HA; Ca10(PO4)6(OH)2 was well perused owing to its similarities with body hard tissues and its use as a bone replaced material cause of its bone bonding ability (Shafiei, Behroozi, et al., 2012).apatite with the formula of (FA; Ca10 (PO4)6F2) is also known as a bone repairing biomaterial, with antibacterial activities and significant biocompatibility features, which are also obvious illustrations of FA nanoparticles (Okazaki et al., 1999). Hydroxyapatite demonstrates poor thermal stability by parsing into Tcp; [Ca3(Po4)2], Tricalcum Phosphate at the thermal range further than 1200 °C, which causes problems in long term usage in ceramics and metallic implants in bones, dental roots

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implants. Beyond this, Fluorapatite can keep its stability at temperatures higher than 1000 °C and up to 1400 °C (Chen & Miao, 2005). Due to the higher solubility of Hydroxyapatite in comparison with Fluorapatite, FA indicates better stability in chemical and structural features than HA, hence, there are some parameters that are helpful to improve and control the solubility of HA by substituting the hydroxyl group (OHˉ) with Fluorine (Fˉ). Hydroxyapatite is able to change to Fluorhydroxyapatite and consequently to Fluorapatite by replacing all Hydroxyl groups with Fluorine. Fluorhydroxyapatite was known as FHA, Ca10(PO4)6(OH)2−xFx, in which X can be replaced by different amounts of fluorine, 0<X<1 means the amount of fluoridation. Hence, X=0 means HA, whilst X=1 means FA. Interpolation of fluorine in the structure of pure Hydroxyapatite, or “fluoridation”, diminishes the rate of solubility of HA, by keeping biocompatibility features of HA (Barinov et al., 2003). Several methods are available for preparing HA, FHA and FA to more instant, solid state, Sol-Gel as a wet precipitation are well-known reactions for the preparation of ceramic powders. One of the most striking features is a wet chemical method named Sol-Gel method, which has many benefits such as less pH value and sintering at high temperatures, promoting chemical homogeneity in final products. Furthermore, by reducing the temperature in sintering and calcining within the sol-gel process the powders show better and higher reactivity (Darroudi, E.Hosseini, & Youssefi, 2010). By comparing to other methods there is no doubt that sol-gel method increases hope by preparing nanosized apatite with the very fine size, in that these nanoparticles of HA and FA is well utilized in dental implants in dentistry or orthopedic applications. Therefore, by decreasing the size of nanoparticles of apatites that were prepared by so- gel, they can be easily accepted by the host tissues. This thesis seeks to prepare, characterize and optimize; hydroxyapatite, fluorhydroxyapatite and fluorapatite with method of sol-gel. Sol-gel processing was used to synthesize the FA nanoparticles from HA powder. The advantages of the sol-gel method over other methods are precise control of composition, low processing temperature, and better homogeneity with high purity. There is no doubt that crystallinity shape and size significantly decrease by using biostabilizer of SA. 1.2 Aim of this Research This current study aims to synthesize bio HA and FA powders within the Sol-Gel method for the evaluation of the critical method parameters and their effectiveness to control characteristic features of the ultimate HA and FA nanoparticles, such as morphology and size of crystals, and particles. These powders will be synthesized to

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meet the requirements. Within different temperatures from 25 ᴼC to 1300 ᴼC, as an innovation Sodium alginate is used as bio-stabilize in the solution as a green sol-gel method, in order to compare the different crystallinity sizes. 1.3 Problem Statement Hydroxyapatite has a high rate of solubility that can increase the rate of decay in the biological system, which is a major problem in the structure of HA. On the other hand, poor stability at high temperatures and easy corrosion in acidic fields also cannot be ignored as they place many application limitations in orthopedics and dentistry, while Fluorapatite, compared to HA has lower solubility and better stability in terms of structure and chemically. Modulating the degree of Fluorine replacement in the structure of HA allows for the control of the solubility of the apatite. (Kim, Kim, & Knowles, 2004) Much of the research has focused on the manufacturing FA particles by precipitation techniques or films within thermal spraying methods. Unfortunately, the properties of matter and qualities of the particles and films have proven to be unsatisfactory because of the forming byproducts or because of some technical errors. In this regard, the sol-gel approach has often been adopted to overcome these difficulties. Whilst, the sol-gel technique has been suggested as a promising approach to address several of these problems. Medically, the application of materials and devices with sol-gel coatings is already becoming widespread and is expected to growth in the future years for application within implant materials, drug-delivery systems, grafting of bone and materials with biogenic features with scaffolds and biologically active membranes (Ben-Nissan & Choi, 2006). 1.4 Objectives The main objective is to: As an innovation synthesizing, optimization and characterization of HA and FA within Sol-Gel method by adding sodium alginate into their structure as a bio green stabilizer. Green synthesis method in the producing FA nanoparticle can be an alternative which should be conducted in the first main part of sol-gel method by adding natural biopolymer such as Sodium alginate as a biostabilizer for having better precipitate which lead to have fine particle size. The specific objectives are to:

(1) Synthesize and optimize the FA nanostructures by adding the different amount of fluorine within the structure of HA which produced within the method of the sol-gel.

(2) Characterize and investigate the size of the particles and morphology of the HA, FA by sol-gel method under thermal treatment range of 700 ᴼC for

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calcination and 1300 ᴼC for sintering and comparing the different shapes and sizes between HA and FA by using bio-stabilizer of SA.

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6 REFERENCES Adolfsson, E., Nygren, M., & Hermansson, L. (1999). Decomposition mechanisms

in aluminum oxide–apatite systems. Journal of the American Ceramic Society, 82(10), 2909-2912.

Aftab, T., Khan, M. M. A., Naeem, M., Idrees, M., Siddiqi, T., & Varshney, L.

(2014). Effect of irradiated sodium alginate and phosphorus on biomass and artemisinin production in Artemisia annua. Carbohydrate polymers, 110, 396-404.

Agrawal, K., Singh, G., Puri, D., & Prakash, S. (2011). Synthesis and

characterization of hydroxyapatite powder by sol-gel method for biomedical application. Journal of Minerals and Materials Characterization and Engineering, 10(08), 727.

Azami, M., Jalilifiroozinezhad, S., Mozafari, Masoud, Rabiee, & Mohammad.

(2011). Synthesis and solubility of calcium fluoride/hydroxy-fluorapatite nanocrystals for dental applications. Ceramics International, 37(6), 2007-2014.

Barandehfard, F., Rad, M. K., Hosseinnia, A., Khoshroo, K., Tahriri, M., Jazayeri,

H., Tayebi, L. (2016). The addition of synthesized hydroxyapatite and fluorapatite nanoparticles to a glass-ionomer cement for dental restoration and its effects on mechanical properties. Ceramics International, 42(15), 17866-17875.

Barinov, S., umanov, S., Fadeeva, IV, Bibikov, & V Yu. (2003). Environment effect

on the strength of hydroxy-and fluorohydroxyapatite ceramics. Inorganic materials, 39(8), 877-880.

Ben-Nissan, B., & Choi, A. H. (2006). Sol-gel production of bioactive nanocoatings

for medical applications. Part 1: an introduction. Bernard, L., Freche, M., Lacout, JL , Biscans, & B (1999). Preparation of

hydroxyapatite by neutralization at low temperature—influence of purity of the raw material. Powder technology, 103(1), 19-25.

Blair, H. C., Kahn, A. J., Crouch, E. C., & Jeffrey, J. J. (1986). Isolated osteoclasts

resorb the organic and inorganic components of bone. The Journal of cell biology, 102(4), 1164-1172.

Bose, S., & Tarafder, S. (2012). Calcium phosphate ceramic systems in growth factor

and drug delivery for bone tissue engineering: a review. Acta biomaterialia, 8(4), 1401-1421.

Brinker, C. J., & Scherer, G. W. (2013). Sol-gel science: the physics and chemistry

of sol-gel processing: Academic press.

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